Protein-sulfonyl halide complex ruminant feed material

ABSTRACT

IMPROVED PROTEIN FEED MATERIAL FOR RUMINANTS WHICH IS RESISTANT TO DIGESTIVE BREAKDOWN IN THE RUMEN BUT NOT IN THE ABOSMASUM AND/OR INTESTINES WHICH COMPRISES THE REACTION PRODUCT OF A PROTEIN-CONTAINING FEED MATERIAL AND AN ALKYL OR ARYL SULFONYL HALIDE. EXEMPLARY OF SUCH SULFONYL HALIDES IS P-TOLYL SULFONYL CHLORIDE.

United States Patent 3,711,289 PROTEIN-SULFONYL HALIDE COMPLEX RUMINANT FEED MATERIAL Robert E. Miller, Ballwin, Mo., assignor to Monsanto Company, St. Louis, M0.

N0 Drawing. Filed Oct. 27, 1970, Ser. No. 84,475 Int. Cl. A23k N00 US. Cl. 99-2 R 4 Claims ABSTRACT OF THE DISCLOSURE Improved protein feed material for ruminants which is resistant to digestive breakdown in the rumen but not in the abomasum and/or intestines which comprises the reaction product of a protein-containing feed material and an alkyl or aryl sulfonyl halide. Exemplary of such sulfonyl halides is p-tolyl sulfonyl chloride.

BACKGROUND OF THE INVENTION Field of the invention This invention relates to a method for improving the feed utilization of ruminant animals. In a particular aspect this invention relates to a method for improving protein utilization in ruminant animals. In a further aspect this invention relates to modified protein feed compositions useful in ruminant nutrition which are resistant to digestive attack in the fluid medium of the rumen.

Description of the prior art The digestive system of the ruminant animal (cattle, sheep, bison, camels, etc.) is designed to permit eflicient use of coarse, fibrous foodstuffs. Because of its particular structure and nature, however, the ruminants digestive system is ineflicient in obtaining nutritional value from protein materials. Principally for this reason it is common practice in ruminant nutrition to supplement the diet of the animal with added protein. The supplemental protein serves to increase the rate of growth of the animal and in the case of sheep promotes wool growth.

The rumen, the largest of the four stomach compartments of the animal, serves as an important location for digestive breakdown of ingested foodstuffs chiefly through the action of microorganisms present therein. However, absorption of most nutrients for metabolic purposes does not occur in the rumen but takes place further along in the alimentary tract, principally in the abomasum and intestines. Ingested food is typically retained in the rumen for from about 12-30 hours during which time it is subject to digestive breakdown by the microorganisms and by the rumen fluid-Much ingested protein material is broken down in the rumen to soluble peptides and amino acids. In turn much of these peptides and amino acids are utilized by the microorganisms present in the rumen fluid thereby removing them as a source of nutrition for the host animal.

Because of the desirability as indicated above of avoiding protein breakdown in the rumen in order to permit absorption in the abomasum and intestines it has been suggested that nutrient protein-containing materials fed to ruminants be treated so as to permit passage without digestive breakdown through the rumen to the abomasum. Suggested procedures have included coating the protein material, for example, with fats and vegetable oils, heat treatment of the protein material and reaction of the protein material with formaldehyde. In any event the treated material must be resistant to digestive breakdown in the rumen fluid, which is a fluid buffered at about pH 6-7 by phosphate-bicarbonate from saliva and carbon dioxide, but subject to breakdown in the acid medium of 3,711,289 Patented Jan. 16, 1973 the fluid of the abomasum which has a pH, due principally to hydrochloric acid secretion, of about 2-4.

OBJECTS It is an object of the present invention to provide a method for improving the feed utilization of ruminant animals.

It is a further object of the present invention to provide a method for improving the protein utilization of ruminant animals whereby protein passes through the rumen without substantial digestive breakdown.

Other objects and advantages of the present invention will be apparent from the specification and appende claims.

SUMMARY OF THE INVENTION DETAILED DESCRIPTION The protein-containing reaction product used in the method of the present invention is the reaction product of a protein-containing nutrient feed material and a sulfonyl halide selected from the group consisting of alkyl halides and aryl sulfonyl halides. Such suitable alkyl sulfonyl halides and aryl sulfonyl halides are represented by the general formula RSO X wherein X is a halo radical, for example, chloro, bromo, and iodo, where R is aryl or alkyl containing, for example, up to about 18 carbon atoms. Examples of suitable sulfonyl halides coming within the above formula are p-tolyl sulfonyl chloride, p-tolyl sulfonyl bromide, p-chorobenzene sulfonyl chloride, p-bromobenzene sulfonyl bromide, p-propylbenzene sulfonyl chloride, benzene sulfonyl chloride, propyl sulfonyl chloride, octadecyl sulfonyl chloride, p-methylcyclohexyl sulfonyl chloride, heptyl sulfonyl chloride, decyl sulfonyl chloride, etc.

The protein-containing nutrient material can be from any suitable source including animal, plant, or synthetic sources such as, for example, silage, grains, nuts, chaffs, casein, soy bean meal, fish meal, peanut meal, beef scraps, pork scraps, linseed meal, milk solids, etc.

The useful reaction products of the present invention are prepared by the interaction of sulfonyl halide and protein nutrient material by any suitable procedure. The reaction is readily carried out in a suitable solvent medium inert to the reactants and the reaction products. Such suitable inert solvents include water, preferably at pH 6.5-7.0, dioxane, aliphatic esters such as ethyl acetate and methyl acetate, petroleum ether, and aliphatic hydrocarbons such as hexane. The reaction may be carried out at any suitable temperature, however, elevated temperatures' above about 70 C. particularly for extended periods should be avoided to minimize degradation of protein material. Temperatures in the range of from about 10 to about 40 C. are typically employed with room temperature being both suitable and practical. The reaction is preferably carried out simply by forming a slurry of the reactants in the solvent medium and agitating, as by stirring, the slurry thereby to permit sufficient reaction of the protein with the sulfonyl halide. The thus treated protein is filtered, washed and then dried as by oven 3 drying, drum drying or simple evaporation to recover the modified protein nutrient material.

It is important in order to insure operability of the present invention that the amount of sulfonyl halide incorporated into the protein material be sufiicient to prevent digestive breakdown to soluble peptides and amino acids in the rumen but insuflicient to prevent digestive breakdown to soluble peptides and amino acids in the abomasum and intestines. This amount will, of course, vary and will depend among other things on the particular protein material, the particular sulfonyl halide of choice, the pH of the solvent of reaction, time and temperature of reaction, the species and age of the animal, and the total makeup of the animal diet. Typically an amount in the range of from about 0.0001 to about 0.001 mole of sulfonyl halide for each gram of protein contained in the protein material is employed with amounts in the range of from about 0.0003 to about 0.0009 mole being generally preferred.

It is understood that the modified ruminant protein feed of the present invention can be fed separately to the animal or it can be used for incorporation in other ruminant feed materials. Illustrative of ruminant feed materials in which the protein material of the present invention may be incorporated are soy bean meal, ground corn, hay, straw, cotton seed hulls, cotton mill waste, feed pulp, silage, oats, barley, cereal, brans, cereal middlings, and combinations thereof. If desired other components, for example, minerals, such as bone meal, salt, and trace minerals, antibiotics and vitamins may be included in the animal feed ration.

The following examples illustrate the effectiveness of sulfonyl halide compositions useful in the present invention in protecting protein-containing material from digestion in the fluid of the rumen While permitting digestion in the fluids of the abomasum and intestines. The small scale in vitro experiments shown in the examples simulate conditions existing in the rumen, in the abomasum, and in the intestines thereby permitting the study of treated protein without the use of live animals and large quantities of feed materials. It is understood that the examples are presented for the purpose of illustration only and the invention is not limited to the compositions or methods shown therein.

EXAMPLE 1 Preparation of treated protein Casein (5.02 grams) was added to a solution of ptolyl sulfonyl chloride (0.44 gram) in water (pH 6.5-7.0) (100 milliliters). The resulting mixture was stirred for about 6 hours at room temperature to permit reaction of p-tolyl sulfonyl chloride with casein. The reaction product was then filtered, washed with water and vacuum dried to obtain protein product containing 0.0004 mole of p-tolyl sulfonyl chloride per gram of casein.

Rumen digestion test To 10 milliliters of rumen fluid from fasted sheep contained in a 50 milliliter glass flask was added 10 milliliters of a buttered solution of the following composition.

Buffer solution in grams per liter The resulting mixture was adjusted to pH 6.8 (4 N hydrochloric acid). To the bulfered rumen fluid was added milligrams of the p-tolyl sulfonyl chloride treated protein prepared above. The flask was then purged with nitrogen, stoppered (pressure release valve) and heated at 38 C. on a water shaker bath. Protection of protein from digestion was determined by ammonia production with a lower amount of ammonia production indicating a lower amount of digestion of protein. Ammonia production was determined after 6 hours and after 24 hours with results being presented in Table 1.

Abomasum digestion test Gastric fluid was prepared as follows: NaCl (2 grams) was dissolved in sufl'icient water to give a total volume of 950 milliliters. Pepsin (3.2 grams) was added thereto. Concentrated hydrochloric acid (7 milliliters) was added to the resulting medium and the pH of the medium was then adjusted to 2.0 with aqueous sodium hydroxide.

To a glass flask containing 20 milliliters of the gastric fluid prepared as above were added 60 milligrams of ptolyl sulfonyl chloride treated casein prepared above. The glass flask containing the resulting mixture was stoppered with pressure release valves and heated at 38 C. on a Water shaker bath for 2 hours. Digestion of protein was then determined by ammonia analysis, the greater amount of ammonia produced the greater the amount of protein digested. The results are given in Table l.

Intestine digestion test Intestinal fluid was prepared as follows: NaCl (2 grams) was dissolved in suflicient water to give a total volume of 950 milliliters. Pepsin (3.2 grams) was added thereto. Concentrated hydrochloric acid (7 milliliters) was added to the medium and the pH of the medium was then adjusted to 7.0 with 0.1 N sodium hydroxide. Pancreatin (10 milligrams per milliliter of medium) was added to the resulting medium.

To a glass flask containing 20 milliliters of the intestinal fluid were added 60* milligrams of p-tolyl sulfonyl chloride treated casein prepared above. The glass flask was stoppered with pressure release valves and heated at 30 C. on a water shaker bath, for the prescribed period of time. Digestion of protein was determined by ammonia analysis, the greater amount of ammonia produced the greater amount of protein digested. The results are given in Table l.

EXAMPLES 2-6 Following the general procedures and-tests of Example 1 sulfonyl halide treated casein samples were prepared and tested. The results are presented in Table 1.

In the same manner other protein-containing materials may be reacted with sulfonyl halides to protect the protein material from digestive breakdown in the rumen while permitting its digestions in the abomasum and intestines.

EXAMPLE 7 Octadecyl sulfonyl chloride treated casein containing 0.0006 mole octadecyl sulfonyl chloride per gram of protein is resistant to digestion in the rumen but is readily digested in the abomasum and intestines.

EXAMPLE 8 Heptyl sulfonyl bromide treated casein containing 0.0003 mole of heptyl sulfonyl bromide per gram of protein is resistant to digestion in the fluid of the rumen but is readily digested in the fluids of the abomasum and intestines.

Since many embodiments of this invention. may be made and since many changes may be made in the embodiments described, the foregoing is to be interpreted as illustrative only and the invention is defined by the claims appended hereto.

TABLE 1 Percent total protein digested Moles of sul- Ammonia N Ammonia N fonyl harumen aiter Ammonia N intestine after Ex. lide/gram abomasum No. Sulionyl halide of casein 6 hrs. 24 hrs. after 2 hrs. 4 hrs. 20 hrs.

1 p-Tolyl sulfonyl chloride 0. 0004 41 84 98 105 2 p Chlorobenzene sulfonyl choride 0004 28 111 100 141 3 p-Tolyl sulfonyl chloride 0. 0008 1 4 35 41 58 4 do.- 0. 0016 7 22 17 18 5 do 0. 0016 5 3 8 6 do 0. 005 7 77 90 95 Due at least in part to decomposition of rumen microorganisms.

I claim:

3. The method of claim 2 wherein the aryl sulfonyl 1. A method for improving the protein utilization of 15 chloride is p-tolyl sulfonyl chloride.

ruminant animals which comprises feeding the ruminant animal a complex of a protein-containing nutrient feed material selected from the group consisting of silage, grain, nuts, chaffs, casein, soy bean meal, fish meal, peanut meal, beef scraps, pork scraps, linseed meal and milk solids and a sulfonyl halide of the formula RSO X wherein X represents a halo radical and R represents a radical selected from the group consisting of alkyl having up to 18 carbon atoms and aryl having up to 18 carbon atoms, the amount of sulfonyl halide in said complex being in the range of from about 0. 0001 to about 0.001 mole per gram of protein, said amount being sufiicient to render said feed material resistant to digestive breakdown in the fluid of the rumen but insufficient to prevent substantial digestive breakdown in the fluids of the abomasum and of the intestines.

2. The method of claim 1 wherein the sulfonyl halide is an aryl sulfonyl chloride.

4. The method of claim 1 wherein the amount of sulfonyl halide is in the range of from about 0.0003 to about 0.0009 mole per gram of protein.

References Cited UNITED STATES PATENTS NORMAN YUDKOFF, Primary Examiner H. H. BERNSTEIN, Assistant Examiner US. Cl. X.R. 

